Insecticidal o,o-dialkyl-beta-phenylthiovinyl phosphates

ABSTRACT

VINYL PHOSPHATES OF THE FORMULA:   1-X,4-((R-O-)2-P(=O)-O-CH=CH-S-)BENZENE   WHERE R IS ALKYL OF 1 TO 4 CARBON ATOMS AND X IS HYDROGEN, HALOGEN OF ATOMIC NUMBER 17 TO 35 OR ALKYL OF 1 TO 4 CARBON ATOMS ARE USED AS INSECTICIDES AND MOLLUSCICIDES.

INSECTICIDAL 0,0-DIA KYL-p-PHENYLTHIO- VINYL PHOSPHATES Melancthon S. Brown, Berkeley, Calif., assignor to Chevron Research Company, San Francisco, Calif. N Drawing. Original application Feb. 12, 1968, Ser. No. 704,557, now Patent No. 3,584,084. Divided and this application Dec. 4, 1970, Ser. No. 128,600

Int. Cl. A01n 9/36' US. Cl. 424-216 7 Claims ABSTRACT OF THE DISCLOSURE Vinyl phosphates of the formula:

where R is alkyl of 1 to 4 carbon atoms and X is hydrogen, halogen of atomic number 17 to 35 or alkyl of 1 to 4 carbon atoms are used as insecticides and molluscicides.

CROSS REFERENCE TO RELATED APPLICATION This application is a division of application Ser. No. 704,557, filed Feb. 12, 1968, now US. Pat. No. 3,584,-

X and R are as defined previously. This reaction will normally be carried out at temperatures in the range of 20 to 150 C. and atmospheric or autogenous pressures. An inert solvent such as benzene, toluene, methylene chloride, chloroform, ethyl ether, etc., will normally be. used. The reaction time will usually be about 5 minutes to 48 hours.

The aldehyde reactant (1) may be prepared by reacting a p-substituted phenylsulfenyl halide, preferably a chloride, with acetaldehyde and chlorinating the carbon atom of the resulting product which is between the sulfur and the carbonyl group with a chlorinating agent such as sulfuryl chloride or chlorine. It may also be prepared by reacting a p-substituted alkali metal phenate with chloroacetaldehyde and chlorinating the resulting product as described above. A third procedure to prepare the aldehyde reactant is to react a p-substituted phenylsulfenyl halide with an alkylvinyl ether, react the resulting alkyl- 1-halo-2-phenylthio ether with water and chlorinate that reaction product as described above.

EXAMPLES The following examples illustrate specific vinyl phosphates of this invention and their preparation. These examples are in no way intendedto limit the invention described herein. Unless otherwise indicated percentages are by weight.

Example 1 A benzene solution of 14.45 g. 2-chloro-2-p-chlorophenylthioacetaldehyde was put in a flask and heated to reflux. 9 g. of trimethyl phosphite in 10 ml. benzene was then added dropwise to the refluxing mixture. The total mixture was refluxed for 4 hrs. The benzene and excess phosphite were removed at 60 C. under water vacuum to give 19.25 g. of 0,0-dimethyl-fl-p-chloro- 3,796,799 Patented Mar. 12, 1974 TABLEI Element analyses, percent Calculated Found Compound 01 S P 01 S P 0,0-diethyl-B-p-chlorophenylthiovinyl phosphate 11.0 9.92 11.7 10.24 0,0-dimethyl-B-p-tolylthlovinyl phosphate 11.63 11.30 11.77 10.62 0,0-diethyl-/3-p-tolylthiovlnyl phosphate.-. 10 57 10.25 10 61 10 10 0,0-diisopropyl-B-p-tolyl vinyl phosphate 9.70 9.39 9.31 8.40 0,0-diisopropyl-fl-p-ehlorophenylthiovlnyl phosphate.-- 10.1 9.13 10.55 9.11 0,0-di-n-butyl-fi-p-chlorophenylthiovinyl phosphate.-- 9.36 8.45 9.24 8.31 0,0-diethyl-B-phenylthiovlnyl phosphate 11.1 10.75 11.05 10.60 0,0-dimethyl-B-phenylthlo- I I vinyl phosphate 12.3 11.9 12.01. 12.0

UTILITY The phosphates of this invention have exhibited exceptional abilities for controlling insects and mollusks. In general their molluscicidal activities are unexpectedly better than those of structurally related compounds. Also, the residual miticidal activities of these phosphates, especially those wherein X in the above formulae is chlorine, are vastly superior to most structurally related compounds.

The terms insecticide and insec as used herein refer to their broad and commonly understood usuage rather than to those creatures which in the strict biological sense are classified as insects. Thus the term insect not only includes small invertebrate animals 'belonging to the class Insecta, but also other classes of arthropods whose members are segmented invertebrates having more or fewer than six legs such as mites, ticks, spiders, centipedes, worms and the like.

The term residual as used herein refers to the 1ongevity of the effectiveness of the phosphate. It expresses the ability of controlling organisms which are not contacted by the phosphate at the time it is applied to the organisms environment.

Phosphates of this invention were tested as insecticides against files, aphids, mites and cockroaches. They were effective against all of these organisms. The unusual residual miticidal activity of these compounds was demonstrated by testing representative phosphates as follows:

A 1% acetone solution of the test phosphate was diluted with water to a concentration of 1000 p.p.m. This mixture was sprayed on 4 replicate pinto bean plants at a dosage of 1000 p.p.m./ gaL/acre. After spraying, the bean plants were placed in a greenhouse and allowed to weather for 24 hours. The plants were then infested with two-spotted mites (Tetranychus telarius L.). After 24 hours a mortality reading was taken on 20 randomly chosen mites. The percent dead out of 20 are represented in Table II. Dimethyl-fi-chloro-p-p-chlorophenylthiovinyl phosphate was also tested by this procedure as a comparison compound. Its percent control is also reported in Table H.

The mol'luscicidal activities of representative phosphates of this invention were determined by contacting common garden snails (Helix spp.) with filter papers impregnated with 20 mgs. of the test phosphate. Two replicates were used with 5 snails per replicate. Mortality readings were made after 24 hours exposure. The effectiveness of each compound, reported as percent control pp sin Ta e ,II. m ylrfih1Q -fi-p- Q p ny thiovinyl phosphate was tested by this procedure as a comparison compound. Its percent control is also reported in Table III,

TABLE II.RESID UAL MITICIDAL ACTIVITY chlorophenylthiovinyl phosphate It was also discovered that the vinyl phosphates of this invention are significantly less toxic to mammals than corresponding phosphates having a methyl 'substituent on the a-carbon atom. For instance in oral applications using laboratory rats, Qo-dimethyl-a-methyl-fi-p-chlorophenylthiovinyl phosphate was about 45 to 50 times as toxic as 0,0-dimethyl-B-p-chlorophenylthiovinyl phosphate. In like tests, 0,0diethyl-tx-methyl-fl-p-chlorophenylthiovinyl phosphate was about 5 times as toxic as 0,0-diethyl- 3-pchlorophenylthiovinyl phosphate. This fact makes the compounds of this invention more desirable than their corresponding a-methyl substituted analogs for use in mammalian environment.

Aside from the specific formulations of the phosphates of this invention as reported in the foregoing tests, these phosphates may be dispersed in or upon other inert liquid and solid carriers. The solid carriers, such as clay, may be in the form of dusts, granules or wettable powders. The liquid diluents which may be used in formulating these phosphates include organic compounds such as acetone, benzene, and toluene. Pesticidal formulations of these phosphates may also contain dispersing agents, emulsifying agents, stickers, stabilizers and the like. These phosphates may be applied individually or in mixtures with other phosphates of this invention, and may also 'be used with other active compatible toxicants in the formulation of pesticidal compositions.

These phosphates may be applied in insecticidal or molluscicidal quantities directly to the organism. Or, they 4 may be applied to any environmental area which hosts insects or mollusks or are susceptible to their attack. For example, they may be sprayed or otherwise applied directly to plants or other hosts, may be applied to plant seeds, sprayed upon soil or other plant environments or used in similar ways to control insects and mollusks.

As will be evident to those skilled in the art, various modifications on this process can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

What is claimed is:

1. A method of killing insects which comprises contacting said insects with an insecticidally effective amount of a compound of the formula wherein R is alkyl of l to 4 carbon atoms, and X is hydrogen, halogen of atomic number 17 to 35 or alkyl of 1 to 4 carbon atoms.

2. The method of claim 1 wherein X is chlorine, hydrogen or methyl.

3. The method of claim 2 wherein R is methyl or ethyl.

4. The method of claim 3 wherein R is methyl and X is chlorine.

5. The method of claim 3 wherein R is ethyl and X is chlorine.

6. An insecticidal composition comprising an insecticidally effective amount of a compound of the formula wherein R is alkyl of 1 to 4 carbon atoms, and X is hydrogen, halogen of atomic number 17 to 35 or alkyl of 1 to 4 carbon atoms and a biologically inert carrier.

7. The composition of claim 6 wherein X is chlorine, hydrogen or methyl and R is methyl or ethyl.

References Cited UNITED STATES PATENTS 2,864,740 12/ 8 Diveley 260-948 X 3,584,084 6/1971 Brown 260-949 FOREIGN PATENTS 6413169 5/ 1965 Netherlands 260949 ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner UNITED sTATEs PATENT OFFICE 7 CERTIFICATE OF CORRECTION Patent No. 3,79 ,799 Dated March 12, 1974 Inventor) hela-ncthon S. Brown It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' FIELD OF INVENTION I .1

This invention relates to novel vinyl phosphates and I their use as pesticides. More particularly, it concerns a unique group of 0,0-dialkyl-B-phenylthiovinyl phosphates and their use as insecticides and molluscicides.

DESCRIPTION OF INVENTION- Thevi y P p tes of this invention may be repre- 'sented by th .fqr l 1 v I p O i X S-C=C-O-P"' (OR) 2 where R is, alkyl of l to 4 carbon atoms and X is hydrogen, halogen ofatomic number 17. to 35 or alkyl of 1 :to 4 carbon atoms. The R 's may. be the same or different. 'Where R represents propyl or butyl, these radicals are preferably straight chain. X may also be methyl, ethyl, propyl or butyl. Preferably, X is chlorine and R- is methyl or ethyl. Specific examples of vinyl phosphates encompassed within the above genus are 0,0-dimethyl-B-p-chlorbphenylthiovinyl phosphate, 0,0-dimethyl-B-p-bromophenylthiovinylphosphate, 0,0-dimethyl:B- pe-butylphenylthiovinyl phosphate, 0,0-dimethyl-B- p-tolylthiovinyl phosphate, O-methyl-O-ethyl-B-p-tolylthiovinyl phosphate, 0,0+dimethyl 8-p-ethylphenylthiovinyl phosphate, 0,0- diethyl-B-pbromophenylthiovinyl phosphate, 0,0,-di-npropyl-Bpchlorophenylthiovinyl phosphate, 0,0-di-isop-ropyl-+Bphenylthiovinyl phosphate, 0,0-di-n-propyl-B-p-bromophenylthiovinylphosphate and 0,0-di-h-butyl-B-pchlorophenylthiovinyl phosphate.

The 0,0-dialkyl-B-substituted vinyl phosphates of this invention may be prepared by reacting an appropriate aldehyde with a trialkylphosphite. This reaction proceeds according to the following'equation: I

Signed and sealed this 30th day of JulyTl9 7l Attest; I y v MCCOY M. GIBSON, JR. I c. MARSHALL DANN v Attesting Officer Commissioner of Patents 

